EP0139404B1 - Die Aufbereitung von Wasser mit einem Biozid - Google Patents

Die Aufbereitung von Wasser mit einem Biozid Download PDF

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Publication number
EP0139404B1
EP0139404B1 EP84305804A EP84305804A EP0139404B1 EP 0139404 B1 EP0139404 B1 EP 0139404B1 EP 84305804 A EP84305804 A EP 84305804A EP 84305804 A EP84305804 A EP 84305804A EP 0139404 B1 EP0139404 B1 EP 0139404B1
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EP
European Patent Office
Prior art keywords
water
compound
phosphorus compound
phosphorus
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP84305804A
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English (en)
French (fr)
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EP0139404A1 (de
Inventor
Keith Philip Davis
Robert Eric Talbot
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solvay Solutions UK Ltd
Original Assignee
Albright and Wilson Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB838323025A external-priority patent/GB8323025D0/en
Priority claimed from GB838333787A external-priority patent/GB8333787D0/en
Application filed by Albright and Wilson Ltd filed Critical Albright and Wilson Ltd
Priority to AT84305804T priority Critical patent/ATE32330T1/de
Publication of EP0139404A1 publication Critical patent/EP0139404A1/de
Application granted granted Critical
Publication of EP0139404B1 publication Critical patent/EP0139404B1/de
Expired legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/34—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-halogen bonds; Phosphonium salts
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
    • C02F2103/023—Water in cooling circuits

Definitions

  • This invention relates to the treatment of water to control the growth of aquatic microorganisms therein.
  • Aquatic microorganisms in particular bacteria such as Pseudomonas aeruginosa, fungi such as Oscillatoria, and yeasts such as Sacharomyces cerebisiae grow in a variety of water systems such as industrial plant, chemical plant or steel manufacture, brewing, power generation or paper making plant, marine engines, central heating systems, and water used for oil field injection, or for the manufacture of aqueous based products.
  • the organisms cause corrosion and/or fouling.
  • oxidizing biocides such as chlorine or with inorganic biocides such as copper salts or with organic biocides, including quaternary ammonium or phosphonium compounds, with one or more long chain alkyl groups see, for example, EP­A1­0,066,544.
  • a problem with such quaternary compounds is that such compounds give rise to foaming of the water.
  • An essential component of all known quaternary biocides is the presence of at least one long chain alkyl group. Quaternary amines of lower alkyl groups are not effective biocides.
  • phosphines or phosphonium compounds with 1 or more hydroxyalkyl groups attached to each phosphorus atom are highly effective at controlling the aquatic microorganisms.
  • phosphines or phosphonium compounds are highly cost effective and are effective in the absence of long chain alkyl groups, which give rise to foaming problems in biocides of the prior art.
  • the present invention provides a method of treating water systems containing aquatic microorganisms or susceptible to infection therewith, which method comprises adding to said water certain phosphorus compounds containing at least one hydroxyalkyl group attached directly to a phosphorus atom.
  • the phosphorus compound may contain one phosphorus atom and may then be of formula [HORPR'JyX(n-2) wherein n is 2 or 3; y is 1 when n is 2 and is equal to the valency of X when n is 3; R is an alkylene group of 1 to 4, preferably 1, carbon atoms with the hydroxy group attached to the 1, 2, 3 or 4 numbered carbon atom; each R' may be the same or different and represents an alkyl or alkenyl group of 1-4 carbon atoms, or more usually a group of formula HOR-, wherein R is as defined above; and X is anion such that the phosphorus compound is water soluble.
  • the (-ROH) group may be a 1-, or 2-hydroxyalkyl group e.g. a hydroxy methyl, 1 or 2 hydroxy ethyl 1 or 2 hydroxy-propyl or 1 or 2 hydroxy-butyl group; preferably at least one R' is ROH, but may be for example a methyl, ethyl, propyl, iso propyl, or n- sec-, iso- or tert-butyl group.
  • X may be a monovalent anion such as a chloride or bromide, or an organic carboxylate, e.g.
  • an alkane carboxylate preferably of 2-5 carbon atoms such as acetate, bisulphite or bisulphate or an organic sulphonate such as methosulphate or a benzene, toluene or xylene sulphonate or a dihydrogen phosphate, or a divalent anion such as sulphate or sulphite or monohydrogen phosphate or a trivalent group such as phosphate or organic carboxylates with 2 or more carboxyl groups such as citrate.
  • the phosphorus compound may alternatively contain 2 or more phosphorus atoms, so long as the phosphorus compound is water soluble to a concentration of at least 0.5 g/I at 25°C.
  • Such phosphorus compounds contain at least 1 hydroxy alkyl group, usually per phosphorus atom, and preferably at least 2 hydroxyalkyl groups per phosphorus atom.
  • Such hydroxyalkyl groups are preferably of formula ROH, where R is as defined above.
  • the group or groups joining the phosphorus atoms together may of formula -R-, -R-O-, -R- O-R- or -R-NH-R or -R-R"-R- where R is as defined above and R" is the residue formed by removal of two hydrogen atoms, bonded to nitrogen, from a di or polyamide or di or polyamine, such as urea, dicyandiamide, thiourea or guanidine.
  • Such compounds with 2 or more e.g. 3, hydroxyalkyl groups per phosphorus atom may be made by self condensation of compounds with 3 or 4 hydroxyalkyl groups attached to one phosphorus atom, e.g. of formula [HOR P R' n ] y X (n-2) or with a compound of formula R"H 2 such as urea. The condensation can be performed by heating at 40-120°C.
  • the phosphorus compound contains only one phosphorus atom and 3 or 4 hydroxyalkyl groups especially hydroxymethyl groups.
  • Such compounds are made by reacting phosphine with an aldehyde usually formaldehyde or a ketone in the presence of mineral acid usually hydrochloric, sulphuric or phosphoric acid.
  • mineral acid usually hydrochloric, sulphuric or phosphoric acid.
  • the product may be a tris hydroxyalkyl phosphine or tetrakis (hydroxyalkyl) phosphonium salt; however, the latter tends to be converted to the former under aqueous alkaline conditions with small amounts of the dimeric compound with 2 phosphorus atoms and an ROR bridge.
  • the product may contain up to 10% by weight of free aldehyde or ketone, e.g. formaldehyde and up to 10% by weight of acid.
  • the phosphorus compound usually has a pH of 1-6, when in 75% by weight aqueous solution.
  • the phosphorus compounds in which one or more of R 1 are alkyl groups are made from the corresponding alkyl substituted phosphines by reaction with the aldehyde or ketone. To avoid foaming, any alkyl or alkenyl groups present should have less than 5 carbon atoms.
  • biocides according to our invention include tetrakis (hydroxymethyl) phosphonium sulphate, tetrakis (hydroxymethyl) phosphonium chloride and tetrakis (hydroxymethyl) phosphonium phosphate as preferred examples.
  • the phosphorus compound may be added to the water to be treated in an amount effective to inhibit growth of the microorganisms therein.
  • the amount is usually 1-5000, e.g. 1-1000, preferably 5-150 and especially 20-50 parts by weight of compound per million parts by weight of the water.
  • the phosphorus compound may be added in aqueous solution to the water.
  • the pH of the water after treatment is usually 5-10, e.g. 6-9, typically 6-7 or 7.5-9.
  • scale or corrosion inhibitors e.g. phosphonates (including aminomethylene phosphonates), polymaleates, polyacrylates, polymethacrylates, polyphosphates or phosphate esters as scale inhibitors in conventional amounts or inorganic corrosion inhibitors such as soluble zinc salts, nitrite, or sulphite or organic corrosion inhibitors such as benzoate, phosphonate, tannin, lignin, benzotriazoles or mercapto benztriazoles, all used again in conventional amounts.
  • phosphorus compounds in accordance with our invention should not be used in conjunction with chromates.
  • the scale and/or corrosion inhibitors may be added to the water separately from or in association with the phosphorus compound.
  • oxygen scavengers flocculants such as polyacrylamide, dispersants, antifoams such as silicones or polyethylenoxylated antifoams or other biocides such as tin compounds or isothiazolones.
  • the present invention also provides a composition for treating water containing aquatic microorganisms, which comprises any of the aforesaid phosphorus compounds containing at least one hydroxyalkyl group attached to a phosphorus atom, together with one or more other biocides, and/or scale or corrosion inhibitors, oxygen scavengers, flocculants, dispersants, and/or antifoam.
  • Compositions of the invention may contain other biocides in addition to the phosphorus compound.
  • the microorganisms to be treated are usually bacteria, fungi, yeasts and algae that grow in aquatic environments. Included in this classification are sulphate reducing bacteria, e.g. Desulphovibrio, iron bacteria e.g. Gallionella and slime forming bacteria, e.g. Pseudomonas, which last are particularly troublesome in aqueous systems.
  • the water to be treated may be industrial cooling water, e.g. for power stations or chemical plants or for steel or paper or brewing and may be used in closed circuit or in open circuit involving evaporation in cooling towers. Alternatively, the water may be process water, especially process water containing significant sources of nutrients for microorganisms such as process water to paper making plants and breweries. Injection water for oil fields or water used in reverse osmosis plants e.g. to provide industrial processes or boiler feed water, may be treated.
  • aquatic environments which may be treated with the hydroxy-alkyl phosphorus compounds according to the method of the invention are cooling or process water in board mills, fertilizer manufacture, oil refineries, primary metals manufacture, e.g. steel or copper, petrochemicals, rubber manufacture, textile and fabrics industries, industrial gas manufacture, minerals recovery, glass and ceramic manufacture, food industry, leather manufacture, heavy and light engineering, including metal fabrication and automotive engineering, furniture manufacture, electronics industry and surface coatings and adhesives manufacture, and other manufacturing industries.
  • the process is also applicable to the treatment of geothermal water, water in domestic, industrial and institutional central heating and air conditioning systems and water used for hydrostatic testing of pipelines and vessels, swimming baths and as cooling water for ships and marine engines.
  • the invention is also applicable to the control of microbial contamination in a wide variety of aqueous based products.
  • the hydroxy alkyl phosphorus compounds may be added to a variety of solutions and emulsion compositions such as paints, cutting oils, bitumen and tar emulsions, adhesives, weedkillers and insecticides, as well as to solid or concentrated compositions for addition to water in the preparation of such products.
  • the invention therefore, further provides aqueous based products which are subject to microbial spoilage to which has been added a bacteriostatic or bactericidal quantity of one of the aforesaid phosphorus compounds containing at least one hydroxyalkyl group attached to the phosphorus atom.
  • such compositions consist of aqueous solutions, suspensions or emulsions of at least one functional ingredient together with a minor proportion of said phosphorus compound, sufficient to inhibit growth of microorganisms therein.
  • the systems to which the invention is particularly applicable are those involving the circulation or storage of substantial quantities of water under conditions favouring the multiplication of bacteria, especially hardy bacteria such as P. Aeruginosa, e.g., conditions involving maintaining or periodically raising the water to super ambient temperatures favouring bacterial proliferation, or maintaining nutrients for the bacteria in the water systems.
  • the invention is illustrated in the following Examples, in which a phosphorus compound was compared for activity against formaldehyde and a control.
  • the phosphorus compound unless stated to the contrary, was a 75% by weight aqueous solution oftetrakis (hydroxymethyl) phosphonium sulphate which solution is referred to herein as THPS and which contained 0.4% free formaldehyde and had a pH of 4.
  • THPS tetrakis (hydroxymethyl) phosphonium sulphate
  • the formaldehyda comparison was used in 40% aqueous solution. All dose levels are expressed in parts per million by weight of the aqueous biocide solution, based on the weight of water treated, unless otherwise stated.
  • test medium was divided into 50 ml portions. One portion was kept as a control and the other portions were dosed with various levels of THPS solution and, for comparative data, a proprietary isothiazolone based biocide. After incubating for 16 hours at room temperature, the bacterial levels in each portion were measured by a standard plate count procedure. The results were as follows:-
  • THPS is extremely effective against Pseudomonas Aeruginosa and, in fact, gives a better performance, in this test, than the proprietary isothiazolone based product.
  • a sample of recirculating water from a heavily infected industrial cooling system was used as a source of micro-organisms for this test.
  • the microbiological population was found to be mixed but the predominant organism was a gram negative rod-shaped bacterium, not specifically identified.
  • test medium containing over 10 7 bacteria per ml, was made up by mixing the infected cooling water, as above, with tap water from South Staffordshire, England, previously dechlorinated by the addition of a small excess of sodium thiosulphate.
  • the test medium was divided into 50 ml portions and one portion was kept as a control. The other portions were dosed with various levels of THPS. After incubating for 16 hours at room temperature the bacterial levels in each portion were measured by a standard plate count procedure. The results were as follows:-
  • Formaldehyde at dose levels sufficient to prevent bacterial growth, is objectionable on grounds of smell and of chemical reactivity, and is not, therefore, used commercially.
  • a sample of recirculating water from a heavily infected industrial cooling water system was used as a source of micro-organisms for this test.
  • the microbiological population was found to be mixed but the predominant organism was identified as Bacillus Cereus.
  • test medium was divided into 50 ml portions four of which were kept as controls.
  • the pH values of the four controls were adjusted, by dropwise addition of 0.1 N sodium hydroxide solution or 0.1 N hydrochloric acid to the required values.
  • each was dosed with the appropriate level of THPS and its pH was quickly adjusted to the required value. All of the portions of test medium were incubated at 30°C for 19 hours. The bacterial levels were then measured by a standard plate count procedure. The results were as follows:-
  • THPS is fully effective as a bactericide over the full range of Ph values commonly found in cooling water systems.
  • the cooling system was in continuous use and immediately prior to the trial the bacteria level in the recirculating water as measured by standard plate count procedure, was about 10 6 per ml. A shot dose of 120 ppm THPS solution was added to the system water and after 3 hours the bacterial level in the recirculating water had fallen to about 200 per ml. No problem with foaming was experienced.
  • This example illustrates the effectiveness of THPS as a bactericide in a large industrial cooling system.
  • the cooling system was in continuous use and immediately prior to the trial the bacterial level in the recirculating water, as measured by a standard plate count procedure, was 2000 per ml. A shot dose of 96 ppm THPS solution was added to the system water and within 1 hour the bacterial level had been reduced to 100 per ml. No problem with foaming was experienced.
  • This example further illustrates the effectiveness ofTHPS as a bactericide in an industrial cooling water system.
  • THPC tetrakis(hydroxymethyl) phosphonium chloride added as an 80% by weight aqueous solution
  • THPP tetrakis(hydroxymethyl)phosphonium phosphate added in aqueous solution containing a concentration of tetrakis(hydroxymethyl) phosphonium group equivalent to 750 g tri[tetrakis(hydroxymethyl) phosphonium] phosphate per kg of solution
  • chloride and phosphate salts of the THP moiety are at least as effective as biocides as THPS against cooling water bacteria at pH 6.6.
  • a liquid scourer formulation was made up according to the following recipe:
  • An active culture of Pseudomonas Aeruginosa was made up in nutrient broth as described in Example 1. 0.2 ml of the final sub-cultured broth was added to 50 ml of the above formulation to give a bacterial concentration of approximately 10 8 per ml. The infected formulation was divided into three equal portioms, the first portion was used as a control (i.e. no biocide added) and to the second and third portions THPS was added to give levels of 500 ppm and 1000 ppm, in the formulation, respectively.
  • a liquid detergent formulation was made-up according to the following recipe:-
  • Example 8 The bactericidal test procedure in Example 8 was repeated using this formulation and results were as follows:
  • An adhesive paste formulation was made up according to the following recipe:
  • a dispersant formulation was made up according to the following recipe:
  • the compounds of the present invention have the capacity to react with dissolved oxygen as shown by the following experiments:
  • the experiment was set up at 25°C and 0.1 N sodium hydroxide solution was added in a sufficient quantity so that when 500 ppm of THPS was subsequently added, the solution pH was about 9.
  • the dissolved oxygen level was about 10 ppm and the rate of reaction of scavenger with dissolved oxygen at pH 9 was very slow. However, on reducing the pH to below 7, by the addition of 0.1 N hydrochloric acid, the reaction rate increased. When the pH was 6.2, the concentration of dissolved oxygen in the water was reduced from 10 ppm to zero ppm in 50 seconds.
  • LTBPC lauryltributyl phosphonium chloride
  • THPS is more effective than LTBPC as a bactericide against cooling water bacteria.
  • Fungal spores isolated from an industrial cooling water system were used in this test. The variety of fungus was not specifically identified, but was thought to be of the genus Aspergillus.
  • THP moiety is an active fungicide.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental Sciences (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Agronomy & Crop Science (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Water Treatment By Sorption (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)

Claims (17)

1. Verfahren zur Behandlung wässeriger Systeme, die durch eine Infektion von in Wasser lebenden Mikroorganismen gefährdet sind, mit dem Ziel einer Inhibierung des Wachstums derselben, bei welchem Verfahren zu diesen wässerigen Systemen zumindest eine Phosphorverbindung der Formel [HORPR'nl,X("-1) zugesetzt wird, worin n für 2 oder 3 steht; y 1 bedeutet, wenn n für 2 steht, und gleich der Wertigkeit von X ist, wenn n für 3 steht; R für eine Alkenylgruppe mit 1 bis 4 Kohlenstoffatomen steht; jeder Rest R' gleich oder verschieden sein kann und für eine Alkyl- oder Alkylengruppe mit bis zu 4 Kohlenstoffatomen oder eine Gruppe der Formel HOR- steht, in welcher R die oben genannte Bedeutung hat; und X für ein Anion steht, sodaß die Phosphorverbindung wasserlöslich ist.
2. Verfahren nach Anspruch 1, bei welchem R für eine Methylengruppe steht.
3. Verfahren nach Anspruch 1 oder 2, bei welchem jede R'-Gruppe für eine HOR-Gruppe steht.
4. Verfahren nach Anspruch 3, bei welchem n=3.
5. Verfahren nach Anspruch 4, bei welchem X für ein Sulfat, Chlorid- oder Phosphat-Anion steht.
6. Verfahren nach Anspruch 1, bei welchem die Phosphorverbindung eine Verbindung mit mindestens 2 Phosphoratomen pro Molekül ist, die durch Kondensation einer Verbindung der in Anspruch 1 dargelegten Formel entweder allein oder in Gegenwart von Harnstoff, Dicyanidamid, Thioharnstoff oder Guanidin gebildet ist.
7. Verfahren nach irgendeinem der vorhergehenden Ansprüche, bei welchem die Phosphorverbindung in einer Menge von 1 bis 1000 Gew.-Teilen pro Million, bezogen auf das zu behandelnde Wasser, zugesetzt wird.
8. Verfahren nach Anspruch 7, bei welchem die Konzentration der Phosphorverbindung in dem wässerigen System zwischen 5 und 150 Gew.-Teilen pro Million gehalten wird.
9. Verfahren nach irgendeinem der vorhergehenden Ansprüche zur Behandlung industrieller Kühl-oder Prozeßwässer.
10. Verfahren nach Anspruch 9 zur Behandlung von Kühlwasser in Kraftwerken, chemischen Anlagen, Stahl- oder Paperfabriken oder Brauereien.
11. Verfahren nach Anspruch 9 zur Behandlung von Einpreßwasser für Ölfelder.
12. Verfahren nach irgendeinem der Ansprüche 1 bis 8 zur Behandlung von geothermischem Wasser oder Wasser in Zentralheizungssystemen, Klimaanlagen, zur Verwendung bei hydrostatischen Untersuchungen, in Schwimmbädern oder als Kühlwasser für Schiffe oder Meerwassermaschinen.
13. Zusammensetzung zur Verwendung bei dem Verfahren nach irgendeinem der vorhergehenden Ansprüche, bestehend im wesentlichen aus einer Verbindung der in Anspruch 1 angegebenen Formel oder einem Kondensat derselben in Verbindung mit mindestens einem anderen Wasserbehandlungsadditiv, ausgewählt aus den Kesselstein- und Korrosionsinhibitoren, Flockungsmitteln, Dispergiermitteln, Schaumverhinderern, Sauerstoffaufnehmern und Biociden.
14. Verfahren nach Anspruch 1, bei welchem eine Zusammensetzung nach Anspruch 13 zu Wasser zugesetzt wird.
15. Produkt auf wässeriger Basis, das in Abwesenheit zugesetzter Biocide gegen mikrobielle Kontamination empfänglich ist und das eine wässerige Suspension, Lösung oder Emulsion von zumindest einem funktionellen Bestandteil enthält, welches Produkt nach einem Verfahren nach irgendeinem der Ansprüche 1 bis 8 zur Inhibierung oder Verhinderung des Wachstums der Mikroorganismen darin behandelt worden ist.
16. Produkt auf wässeriger Basis nach Anspruch 15, das eine Anstrichfarbe, ein Schneidöl, eine Bitumen- oder Teeremulsion, einen Kleber, ein Unkrautvertilgungsmittel oder Insekticid darstellt.
17. Feststoff oder konzentrierte wässerige Mischung, die einen funktionellen Bestandteil und eine Verbindung mit der in Anspruch 1 angegebenen Formel oder ein Kondensat derselben enthält, welche Mischung bei Zusatz vmn Wasser eine Zusammensetzung auf wässeriger Basis nach einem der Ansprüche 15 oder 16 ergibt.
EP84305804A 1983-08-26 1984-08-24 Die Aufbereitung von Wasser mit einem Biozid Expired EP0139404B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84305804T ATE32330T1 (de) 1983-08-26 1984-08-24 Die aufbereitung von wasser mit einem biozid.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB8323025 1983-08-26
GB838323025A GB8323025D0 (en) 1983-08-26 1983-08-26 Biocidal water treatment
GB8333787 1983-12-16
GB838333787A GB8333787D0 (en) 1983-12-19 1983-12-19 Biocidal water treatment

Publications (2)

Publication Number Publication Date
EP0139404A1 EP0139404A1 (de) 1985-05-02
EP0139404B1 true EP0139404B1 (de) 1988-02-03

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US (1) US4673509A (de)
EP (1) EP0139404B1 (de)
KR (1) KR910009128B1 (de)
AU (1) AU563765B2 (de)
CA (1) CA1245126A (de)
DE (1) DE3469162D1 (de)
FI (1) FI76239C (de)
GB (1) GB2145708B (de)
MY (1) MY101829A (de)
NO (1) NO159163C (de)
SA (1) SA91120147B1 (de)

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GB2145708A (en) 1985-04-03
NO159163B (no) 1988-08-29
FI843357A0 (fi) 1984-08-24
KR850001893A (ko) 1985-04-10
FI843357A (fi) 1985-02-27
GB8421547D0 (en) 1984-09-26
MY101829A (en) 1992-01-31
AU3247384A (en) 1985-02-28
FI76239C (fi) 1988-10-10
DE3469162D1 (en) 1988-03-10
FI76239B (fi) 1988-06-30
GB2145708B (en) 1987-02-04
CA1245126A (en) 1988-11-22
US4673509A (en) 1987-06-16
AU563765B2 (en) 1987-07-23
NO159163C (no) 1988-12-07
KR910009128B1 (ko) 1991-10-31
EP0139404A1 (de) 1985-05-02
NO843399L (no) 1985-02-27

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